KR20230042205A - Aspartic polyurea resin system and paint composition having marine antifouling function - Google Patents

Abstract

여기에서, X는 폴리아스파르테이트 수지에서 유래하고, Y는 이소시아네이트류 경화제에서 유래하고, R은 항균 방오 기능을 갖는 기이다. 본 출원에 따른 아스파틱 폴리우레아 수지 시스템은 높은 기계적 강도, 낮은 표면 에너지, 우수한 항균성 등의 특성을 갖는다. 이에 의해 형성된 코팅층은 우수한 방오 효과, 내마모성, 내충격성 및 내식성, 기재에 대한 우수한 습윤성, 높은 접착력 등 많은 장점을 갖는다. 따라서 해양 선박, 해양 엔지니어링 플랫폼, 해저 케이블, 원자력 발전소 송수관 등에 대규모로 사용할 수 있으며 실용적인 응용 가치가 매우 높다.The present application discloses an aspartic polyurea resin (binder) system and a coating composition having a marine antifouling function. The aspartic polyurea resin system includes a polymer having a structure of the following formula.

Here, X is derived from a polyaspartate resin, Y is derived from an isocyanate curing agent, and R is a group having an antibacterial and antifouling function. The aspartic polyurea resin system according to the present application has properties such as high mechanical strength, low surface energy, and excellent antimicrobial properties. The coating layer formed thereby has many advantages, such as excellent antifouling effect, abrasion resistance, impact resistance and corrosion resistance, excellent wettability to a substrate, and high adhesive strength. Therefore, it can be used on a large scale such as marine vessels, marine engineering platforms, submarine cables, and water pipes of nuclear power plants, and has a very high practical application value.

Description

Aspartic polyurea resin system and paint composition having marine antifouling function

This application claims priority to a Chinese patent application filed on September 15, 2021 with application number 202111083499.3 and titled "Aspartic polyurea resin system and paint composition having marine antifouling function".

This application belongs to the technical fields of functional polymeric resins and functional paints, and relates to paints. More specifically, it relates to an aspartic polyurea resin (binder) system and a paint composition having a marine antifouling function.

Marine life pollution causes serious problems, such as increasing fuel consumption on ships, blocking water pipes in nuclear power plants, and accelerating corrosion on metal surfaces. Marine antifouling materials are the first line of defense to protect marine equipment from corrosion by marine organisms, and are an important guarantee for ensuring the smooth progress of mankind's marine development and utilization activities.

Humanity has long struggled with marine life attachment. In the 1960s, tributyltin (TBT) coatings with extensive antifouling properties were introduced. However, TBT is severely toxic to non-target organisms and was banned outright in 2008. Current typical antifouling coatings are tin-free, self-polishing paints that replace organotin with copper, zinc, etc., but coatings containing copper are specific to some deposits, and antifouling enhancers such as Irgarol 1051, copper pyrithione, isothiazolone, etc. Additions should be made to compensate for deficiencies. However, these technologies still release antifouling agents that pollute the marine environment, and the release of the antifouling agents forms a saponification layer, which makes the surface of the coating film rough and is not conducive to reducing resistance and saving energy.

In recent years, a non-toxic, non-staining anti-fouling coating layer has been attracting attention. The antifouling material with low surface energy has a hydrophobic structure, and a superhydrophobic layer is formed on the surface. As a result, marine organisms are not adsorbed on the surface of the material or the adsorption is not strong, and they are eliminated under the action of water flow while the ship is sailing, achieving an antifouling effect. However, regardless of the organic silicone resin or the organic fluorine resin, the scratch resistance of the surface of the coating layer is poor and the price is relatively high, so it is not suitable for large-scale applications. In addition, due to the diversity of marine life, it is difficult to achieve a wide range of antifouling effects with organofluorosilicone coating layers. In particular, in the case of some diatoms, the bacterium C.marina, algae spores and aeruginosa, etc., the larger the contact angle (the more hydrophobic) the surface, the more severe the adhesion.

Polyurea paint has excellent mechanical properties and is excellent in terms of abrasion resistance, impact resistance, corrosion resistance, media resistance, thermal stability, etc., so it is good to apply to areas such as corrosion resistance, waterproofing, wear resistance, damping, protection, and earthquake resistance. Compared with the conventional environmentally friendly coating technology, the modified polyurea paint is a novel marine antifouling paint with great application potential at present.

Recently, third-generation polyurea-polyaspartate polyurea has been attracting attention, and it is mainly formed by a multi-component mixing reaction such as a modified isocyanate prepolymer and a polyaspartate resin. Polyaspartate resin is a secondary amine compound with a unique steric hindrance effect, and its activity is much lower than that of general aliphatic amine resins, and its wettability and adhesion to substrates are remarkably improved. However, based on the currently matured commercially available aspartic polyurea, a polyaspartate resin antifouling system is constructed at the molecular design level to give better antibacterial performance, lower surface energy, and higher mechanical strength, thereby providing better marine performance. Enforcing protection is a relatively big challenge.

The main object of the present application is to compensate for the disadvantages of the prior art by providing an aspartic polyurea resin system having a marine antifouling function, a paint composition, and applications thereof.

In order to achieve the above object, the present application adopts the following technical solution.

An embodiment of the present application provides an aspartic polyurea resin system having a marine antifouling function, which includes a polymer having a structure of the following formula.

Here, X is derived from a polyaspartate resin, Y is derived from an isocyanate curing agent, and R is a group having an antibacterial and antifouling function.

The present application provides an aspartic polyurea resin system having a marine antifouling function. It is mainly formed by the reaction of polyaspartate resins, organic antifouling agents, polyethers, polyisocyanates and organic silicone resins.

Embodiments of the present application further provide a paint composition. Raw materials thereof include polyaspartate resins, organic antifouling agents, polyethers, polyisocyanates, and organic silicone resins.

Embodiments of the present application further provide a method for producing a coating composition, including:

Blending raw materials according to the raw material composition of the coating composition according to any one of the present applications; and

After mixing the polyisocyanate and the organic silicone resin, reacting under a certain temperature in a protective gas atmosphere, and then uniformly mixing with the rest of the raw materials to form a coating composition.

Embodiments of the present application further provide a paint composition prepared according to any one method of the present application.

Embodiments of the present application further provide a coating layer formed of the coating composition according to the present application.

Compared with the prior art, the advantages of the technical solutions according to the embodiments of the present application are as follows.

(1) The provided aspartic polyurea resin system with marine antifouling function has advantages such as low surface energy and excellent antibacterial properties. It not only has excellent antifouling effect and anticorrosive performance, but also is environmentally friendly and has excellent mechanical performance such as abrasion resistance and impact resistance, so the application prospect is wide.

(2) The paint provided is solvent-free, 100% solid, safe, environmentally friendly, odorless, and fast curing. It can be molded by spraying on any curved surface, inclined surface, or vertical surface and does not cause sagging.

(3) The coating layer formed of the paint is dense, seamless, has excellent flexibility, antifouling effect, impact resistance, abrasion resistance, corrosion resistance and chemical resistance (eg acid, alkali, salt, etc.). In addition, it has excellent seawater resistance, earthquake resistance, temperature change stability, wettability to substrates, and adhesive strength, and can be quickly adhered to substrates such as steel and concrete. Therefore, it is suitable for large-scale applications on facilities such as marine vessels, offshore engineering platforms, and water pipes of nuclear power plants, and has very high practical value.

1 is an infrared spectrum of an unmodified polyurea PUA coating layer prepared in Comparative Example 1.
2 is an infrared spectrum of the fluorine-silicon-modified polyurea PUA-FSi coating layer prepared in Comparative Example 2.
3 is an infrared spectrum of the organic antifouling agent-containing polyurea PUA-FSi-N coating layer prepared in Example 1.
4 is a water contact angle photograph of the unmodified polyurea PUA coating layer prepared in Comparative Example 1.
5 is a photograph of the water contact angle of the fluorine-silicon-modified polyurea PUA-FSi coating layer prepared in Comparative Example 2.
6 is a photograph of the contact angle of the organic antifouling agent-containing polyurea PUA-FSi-N coating layer prepared in Example 1.
7 is a photograph of a contact angle of an organic silicon antifouling coating layer (PDMS) formed of a commercially available organic silicon antifouling paint.
8 is a water contact angle comparison diagram of PUA, PUA-FSi, and PUA-Fsi-N coating layers prepared in Comparative Examples 1 and 2 and Example 1 and the PDMS coating layer.
9 is a comparison diagram of adhesive strength of the PUA, PUA-FSi, PUA-Fsi-N coating layer, PDMS coating layer and the epoxy primer prepared in Comparative Examples 1 and 2 and Example 1.
10 is a stress-strain curve of the PUA, PUA-FSi, and PUA-Fsi-N coating layers and the PDMS coating layer prepared in Comparative Examples 1 and 2 and Example 1.
11 is a comparison diagram of Young's modulus of the PUA, PUA-FSi, and PUA-Fsi-N coating layers prepared in Comparative Examples 1 and 2 and Example 1 and the PDMS coating layer.

As described above, in view of the disadvantages of the prior art, the present inventor proposes the technical solution of the present application through long-term research and experiments, and will be described in detail below.

One aspect of the present application provides an aspartic polyurea resin system having a marine antifouling function, which has the following structure.

Here, X is derived from a polyaspartate resin, Y is derived from an isocyanate curing agent, and R is a group having an antibacterial and antifouling function.

Another aspect of the present application provides a method for manufacturing an aspartic polyurea resin system having a marine antifouling function, which includes the following steps. After mixing polyisocyanate and organic silicone resin, reacting at 0 to 80 ° C in a protective gas atmosphere (eg nitrogen atmosphere), then mixing with polyaspartate resin, organic antifouling agent and polyether, and then mixing at 0 to 50 ° C A secondary reaction is performed to obtain the desired product. The mechanism of the reaction is as follows.

X: Fluorosilicone-modified aspartic polyurea resin Y: Fluorosilicon-modified isocyanate curing agent R: A group having an antibacterial and antifouling function.

Furthermore, the mass ratio of polyisocyanate and organic silicone resin here is 0 to 80:20 to 100, preferably 30 to 60:40 to 70.

Further, the mass ratio of polyaspartate resin, organic antifouling agent and polyether here is 0 to 80:0 to 50:0 to 50, preferably 30 to 60:10 to 30:10 to 30.

Further, here, the ratio of the total mass of the polyaspartate resin, the organic antifouling agent and the polyether to the mass of the primary reaction product is 1:0 to 10, preferably 1:0.5 to 2.

It should be noted here that the capacities of polyaspartate resin, organic antifouling agent, polyether, and organic silicone resin are all greater than zero.

Furthermore, the time of the first and second reactions is greater than 0 but within 24 hours, preferably 3 to 12 hours.

Furthermore, the temperature of the first reaction is preferably 20 to 60°C.

Furthermore, the temperature of the secondary reaction is preferably 10 to 40°C.

The aspartic polyurea resin system of the present application is preferably formed by reaction of a fluorine-silicon-modified polyaspartate resin, an organic antifouling agent, a polyether, a polyisocyanate, an organic silicone resin, or the like. It not only combines the advantages of aspartic polyurea resin system, organic silicone polymer, quaternary ammonium salt, and polyether, but also has synergistic effect and antifouling performance due to its low surface energy and excellent antibacterial performance. This is a very surprising level. In addition, it has excellent corrosion resistance, abrasion resistance, impact resistance and strong adhesion, and can be quickly adhered to steel and concrete substrates.

Another aspect of the present application further provides an antifouling structure including the aspartic polyurea resin system having the marine antifouling function.

Furthermore, the antifouling structure may be a single-layer coating layer or a multi-layer coating layer. Here, one coating layer may be mainly composed of the aspartic polyurea resin system having the marine antifouling function.

By forming the antifouling structure on the surface of the substrate, the substrate can be well protected, and a particularly excellent antifouling effect can be realized. The substrate may be made of various materials such as metal, concrete, wood, polymer, or a composite material thereof, but is not limited thereto.

Another aspect of the present application further provides a paint composition comprising any one of the above-described aspartic polyurea resin systems.

In some embodiments, the aspartic polyurea resin system comprises 0.5% to 99% of the dry film weight of the coating composition.

Alternatively, in some embodiments, the sum of the masses of the aspartic polyurea resin system and the one or more antifouling agents constitutes from 0.5% to 99% of the dry film weight of the coating composition. Here, the antifouling agent includes an organic antifouling agent, an inorganic antifouling agent, or a combination thereof, such as metal-dithiocarbamate, copper acrylate, metal antimicrobial agent, metal salt, heterocyclic nitride, urea derivatives, amidos or imides of carboxylic acids, sulfonic and sulfenic acids, salts or esters of carboxylic acids, substituted benzenes, guanidine derivatives, butenolides derivatives, imidazole-containing compounds, and the like.

In some implementations, the coating composition is a solvent free system.

Another aspect of the present application further provides a paint composition. Raw materials thereof include polyaspartate resins, organic antifouling agents, polyethers, polyisocyanates, and organic silicone resins. In addition, it may further include components that are optionally added or not added, such as fillers and adjuvants.

In some implementations, the coating composition is a solvent free system.

In some implementations, the raw materials of the coating composition are 0 to 80 parts by weight of polyaspartate resin, 0 to 50 parts by weight of organic antifouling agent, 0 to 50 parts by weight of polyether, 0 to 80 parts by weight of organic silicone resin and poly 20 to 100 parts by weight of isocyanate, wherein the capacities of polyaspartate resin, organic antifouling agent, polyether and organic silicone resin are all greater than zero.

In some embodiments, the coating composition includes the following components.

The first component includes a polyaspartate resin, an organic antifouling agent, a polyether, and optionally added or not added components (eg, fillers, adjuvants, etc.).

As for the second component, polyisocyanate and organic silicone resin are contained in its raw materials.

In some implementations, the first component includes 0 to 80 parts by weight of polyaspartate resin, 0 to 50 parts by weight of organic antifouling agent, and 0 to 50 parts by weight of polyether.

In some implementations, the raw material of the second component includes 0 to 80 parts by weight of organic silicone resin and 20 to 100 parts by weight of polyisocyanate.

In some embodiments, the mass ratio of the first component to the second component is between 1:0 and 10, wherein the capacity of the second component is greater than zero.

Here, the capacities of the polyaspartate resin, the organic antifouling agent, the polyether, and the organic silicone resin are all greater than zero.

Preferably, the first component includes 30 to 60 parts by weight of polyaspartate resin, 10 to 30 parts by weight of organic antifouling agent, and 10 to 30 parts by weight of polyether.

Preferably, the second component includes 30 to 60 parts by weight of polyisocyanate and 40 to 70 parts by weight of an organic silicone resin.

Preferably, the mass ratio of the first component to the second component is 1:0.5 to 2.

In some embodiments, the polyaspartate resin has the following structure.

Here, R ₁ is an aliphatic hydrocarbon group, the number of carbon atoms thereof is greater than 0 and less than or equal to 100, and R ₂ is a hydrocarbon group containing fluorine or a hydrocarbon group containing silicon, and the number of carbon atoms thereof is greater than 0 and less than 100.

Furthermore, the polyaspartate resin includes a combination of any one or more of a polyaspartate resin, a fluorine-containing polyaspartate resin, a silicon-containing polyaspartate resin, and a fluorine-silicon-containing modified polyaspartate resin. Not limited to this. Here, the modified polyaspartate resin may be produced by the following reaction.

Furthermore, the organic antifouling agent is 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1Hpyrrole-3-carbonitrile (4-bromo-2-(4-chlorophenyl) -5-(trifluoromethyl)-1Hpyrrole-3-carbonitrile), 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1Hpyrrole-3-carbonitrile derivatives, N-( 2,4,6-trichlorophenyl)maleimide (N-(2,4,6-trichlorophenyl)maleimide), copper pyrithione, zinc pyrithione, medetomidine, Medetomidine derivatives, butenolide, butenolide derivatives, alkyl dimethyl benzyl quaternary ammonium salt, trimethoxysilylpropyl-N,N,N-trimethylammonium chloride N,N,N-trimethylammonium chloride), tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride (tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride), dimethyloctadecyl(3-trimethoxysilylpropyl)ammonium chloride ( dimethyloctadecyl(3-trimethoxysilylpropyl)ammonium chloride), dodecylbis(2-hydroxyethyl)methylammonium chloride, bis(2-hydroxyethyl)methyltetradecylammonium chloride (bis( 2-hydroxyethyl) methyltetradecylammonium chloride), but is not limited thereto.

Further, the polyether includes, but is not limited to, a combination of any one or more of polyethylene glycol, polyethylene glycol monomethyl ether, poly(ethylene glycol)methyl ether amine, polypropylene glycol, polypropylene glycol monomethyl ether, and polyether amine. It doesn't work.

In some implementations, the first component further includes a combination of one or more of a filler and an adjuvant.

Furthermore, the first component further includes 0 to 50 parts by weight of a filler and 0 to 20 parts by weight of an auxiliary agent.

Further, the filler includes, but is not limited to, a combination of any one or more of iron sulfur oxide, barium sulfate, titanium dioxide, silicon fine powder, talc powder, and heavy calcium.

Furthermore, the adjuvant includes, but is not limited to, a combination of any one or more of a leveling agent, an antifoaming agent, a dispersing agent, a thickening agent, a coupling agent, and an activating powder.

In some embodiments, the organic silicone resin includes, but is not limited to, a combination of any one or more of the compounds listed below.

Here, n is 10 to 1000.

In some embodiments, the polyisocyanate is hexamethylene diisocyanate trimer, fluorosilicone modified hexamethylene diisocyanate trimer, L-lysine triisocyanate, fluorosilicone modified L-lysine triisocyanate, triphenylmethane triisocyanate, fluorosilicone but is not limited to, combinations of at least one or more of modified triphenylmethane triisocyanates.

Another aspect of the present application further provides a method for producing a coating composition, including:

mixing raw materials according to the raw material composition of the coating composition; and

Polyisocyanate and organic silicone resin are mixed and reacted at 0 to 80 ° C in a protective gas atmosphere (eg nitrogen atmosphere) for 0 to 24 hours, and then uniformly mixed with the rest of the raw materials under a temperature condition of 0 to 50 ° C. Forming a coating composition is included.

In some implementations, the coating composition adopts a two-component design. That is, it includes the above-mentioned first component and second component. Correspondingly, the manufacturing method,

mixing raw materials according to the raw material composition of the coating composition;

Forming a first component by uniformly mixing all the materials constituting the first component;

Forming a second component by mixing polyisocyanate and organic silicone resin and reacting at 0 to 80° C. for 0 to 24 hours in a protective gas atmosphere (eg, nitrogen atmosphere); and

and uniformly mixing the first component and the second component under a temperature condition of 0 to 50° C. to form a coating composition.

The coating composition may be solvent-free. That is, it is 100% solid, safe, environmentally friendly, odorless and fast curing. It can be molded by spraying on any curved surface, inclined surface, or vertical surface and does not cause sagging.

Another aspect of the present application provides a coating layer formed of the coating composition. The coating layer is dense, seamless, has excellent flexibility, and has excellent antifouling effect, impact resistance, wear resistance, corrosion resistance and chemical resistance (eg, acid, alkali, salt, etc.). In addition, it has excellent seawater resistance, earthquake resistance, temperature change stability, wettability to substrates, and adhesive strength, and can be quickly adhered to substrates such as steel and concrete.

Another aspect of the present application provides a method for manufacturing a coating layer, which includes forming a coating layer by coating the coating composition on a surface of a substrate and then drying it. Here, the paint may be applied to the substrate surface by various methods such as scrap coating, spin coating, spray coating, and printing. The substrate may be made of metal, concrete, wood, polymer, or a composite material thereof.

The coating layer of the present application has excellent antifouling effect, abrasion resistance, impact resistance, corrosion resistance, wettability to the substrate, and excellent adhesion, so it can be applied on a large scale on devices or facilities such as marine vessels, marine engineering platforms, and water pipes of nuclear power plants, and can be used for a long time. Excellent antifouling, corrosion resistance, abrasion resistance, corrosion resistance, shock resistance, earthquake resistance, and temperature change stability can be obtained.

In order to more clearly explain the purpose, technical solutions and advantages of the present application, the present application will be described in more detail below with reference to examples. Note that the examples do not limit the protection scope of the present application. In addition, unless otherwise noted, various raw materials used in the following examples can be purchased through a market or obtained by self-production according to guidelines in the art, and various production and test equipment used are also known in the art. It is a known device.

The sources of some of the raw materials used in each of the following Examples and Comparative Examples are as follows.

)Dispersant GA264, Zhongshan Worth Chemical Co., Ltd. (

)

)Pigment 4920 iron oxide sulfur, Langsheng Chemical (China) Co., Ltd. (

)

)Pigment 1250 mesh barium sulfate, Shanghai Kaiinhua Co., Ltd. (

)

)Anti-sagging agent H15, Wacker Chemical (China) Co., Ltd. (

)

)Desiccant A3 powder, Zhengzhou Fulong New Materials Technology Co., Ltd. (

)

Defoamer BYK085, Wacker Chemical (China) Co., Ltd. (瓦克化學(中國)有限公司)

Leveling agent TEGO450, Shanghai Kaiin Chemical Co., Ltd.

) Silane coupling agent KH560, Shandong Qufucheon Guanghua Co., Ltd. (

)

Rheological auxiliary agent BYK410, Wacker Chemical (China) Co., Ltd.

)Light stabilizers 1130 and 292, BASF (China) Limited (

)

)Dehydrator BF-5, Shanghai Heat Trading Co., Ltd. (

)

)Adhesion promoter GB950-90, Shenzhen Peiyang Junyan New Materials Co., Ltd. (

)

Of course, the above-mentioned various raw materials may be substituted with other raw materials listed in this specification.

The test methods used in each of the following examples are as follows.

(1) Nicolet Instrument Co. An infrared test was performed on the raw material and the degree of curing of the coating layer of the examples using an infrared spectrometer (Nicolet iN10) of a U.S.A. Fourier transform microscope.

(2) The water contact angle of the coating layer is tested using a video optical contact angle meter (OCA15EC) from Dataphysics, Germany.

(3) The mechanical properties of the coating were tested using a material tester (Instron 3365) from Instron Corporation, USA.

Comparative Example 1 - A method for preparing a polyaspartate polyurea coating layer includes the following steps.

(1) Preparation of component A of paint: polyaspartate resin (42 parts by weight of Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 12 parts by weight of filler at room temperature After uniformly mixing 0.3 parts by weight of anti-sagging agent, 3 parts by weight of desiccant, 0.2 part by weight of antifoamer A and 0.15 part by weight of antifoamer B, high-speed dispersion for 30 minutes (high-speed dispersion means that the dispersion speed is 1500 r/min or more, the same below) Then, polishing so that the particle size is less than 30㎛, then 0.1 parts by weight of leveling agent A, 0.1 part by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 parts by weight of rheological auxiliary agent, 2 parts by weight of light stabilizer A, light stabilizer 1 part by weight of B and 6 parts by weight of solvent butyl acetate were further added and dispersed at high speed for 10 minutes.

)) 76.5중량부 및 접착촉진제 13.5중량부를 첨가하여 혼합하고, 5분간 고속 분산한다.(2) Preparation of component B of paint: 9.5 parts by weight of solvent butyl acetate, 0.5 parts by weight of dehydrating agent, hexamethylene diisocyanate trimer (Wanhwa Chemical Group Co., Ltd.) at room temperature

)) 76.5 parts by weight and 13.5 parts by weight of the adhesion promoter were added, mixed, and dispersed at high speed for 5 minutes.

(3) Form a paint by uniformly mixing the two components A and B described above at room temperature according to a weight ratio of 1:0.37.

Comparative Example 2 - A method for preparing a fluorine-silicon-modified polyaspartate polyurea coating layer includes the following steps.

(1) Preparation of component A of paint: 42 parts by weight of fluorine silicon modified polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 12 parts by weight of filler, 0.3 part by weight of anti-sagging agent at room temperature Part, 3 parts by weight of desiccant, 0.2 part by weight of antifoamer A and 0.15 part by weight of antifoamer B were uniformly mixed and then dispersed at high speed for 30 minutes at a dispersion speed of 1500 r/min, then polished to a particle size of less than 30㎛, then leveled 0.1 part by weight of A, 0.1 part by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 part by weight of rheological aid, 2 parts by weight of light stabilizer A, 1 part by weight of light stabilizer B and 6 parts by weight of butyl acetate were further added to obtain 10 Disperse at high speed for a minute.

(2) Preparation of component B of the paint: 9.5 parts by weight of butyl acetate, 0.5 parts by weight of a dehydrating agent, 76.5 parts by weight of hexamethylene diisocyanate trimer (Wanhwa Chemical Group Co., Ltd.) and 13.5 parts by weight of an adhesion promoter were added and mixed at room temperature, High speed dispersion for 5 minutes.

(3) Form a paint by uniformly mixing the two components A and B described above at room temperature according to a weight ratio of 1:0.29.

Comparative Example 3 - A method for preparing a fluorine-silicon-modified polyaspartate polyurea coating layer includes the following steps.

(1) Preparation of component A of paint: 42 parts by weight of fluorine silicon modified polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 12 parts by weight of filler, 0.3 part by weight of anti-sagging agent at room temperature Part, 3 parts by weight of desiccant, 0.2 part by weight of antifoamer A and 0.15 part by weight of antifoamer B were uniformly mixed and then dispersed at high speed for 30 minutes at a dispersion speed of 1500 r/min, then polished to a particle size of less than 30㎛, then leveled 0.1 part by weight of A, 0.1 part by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 part by weight of rheological aid, 2 parts by weight of light stabilizer A, 1 part by weight of light stabilizer B and 6 parts by weight of butyl acetate were further added to obtain 10 Disperse at high speed for a minute.

(2) Preparation of component B of paint: 9.5 parts by weight of butyl acetate, 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of hexamethylene diisocyanate trimer (Wanhwa Chemical Group Co., Ltd.), amine-terminated dimethicone (Waker Chemicals (China ) Co., Ltd.) 10 parts by weight and 13.5 parts by weight of an adhesion promoter were added and mixed, and dispersed at high speed for 5 minutes.

(3) Form a paint by uniformly mixing the two components A and B described above at room temperature according to a weight ratio of 1:0.5.

Comparative Example 4 - A manufacturing process of a polyaspartate polyurea coating layer containing a fluorosilicone-modified organic antifouling agent includes the following steps.

(1) Preparation of component A of paint: 42 parts by weight of fluorine silicon modified polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, dodecylbis(2-hydroxyethyl) at room temperature ) 10 parts by weight of methylammonium chloride, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of desiccant, 0.2 parts by weight of antifoamer A and 0.15 parts by weight of antifoamer B were mixed and dispersed at high speed for 30 minutes. The dispersion speed was 1500 r/min, Thereafter, polishing to a particle size of less than 30 μm, 0.1 part by weight of leveling agent A, 0.1 part by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 part by weight of rheological auxiliary agent, 2 parts by weight of light stabilizer A, light stabilizer 1 part by weight of B and 6 parts by weight of butyl acetate were further added and dispersed at high speed for 10 minutes.

(2) Preparation of component B of paint: 9.5 parts by weight of butyl acetate at room temperature, 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wanhwa Chemical Group Co., Ltd.), amine-terminated dimethicone (Waker Chemical (China) Co., Ltd. ) 10 parts by weight and 13.5 parts by weight of an adhesion promoter were added, mixed, and dispersed at high speed for 5 minutes.

(3) Form a paint by uniformly mixing the two components A and B described above at room temperature according to a weight ratio of 1:1.2.

(4) The paint is scrap-coated on a tin plate substrate at room temperature, and the coating film thickness is 200 μm. Its test performance is an activation period of 14 minutes, a surface drying time of 14 minutes at 25° C., a hard drying time of 30 minutes at 25° C., and a hardness of H.

Comparative Example 5 - A manufacturing process of a polyaspartate polyurea coating layer containing a fluorine-silicon-modified organic antifouling agent includes the following steps.

(1) Preparation of component A of paint: 42 parts by weight of fluorine silicon modified polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 2 parts by weight of dispersant, 20 parts by weight of pigment, 10 parts by weight of polyethylene glycol monomethyl ether at room temperature, 12 parts by weight of filler, 0.3 part by weight of anti-sagging agent, 3 parts by weight of desiccant, 0.2 part by weight of antifoamer A and 0.15 part by weight of antifoamer B were mixed and dispersed at high speed for 30 minutes. After polishing as much as possible, 0.1 part by weight of leveling agent A, 0.1 part by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 part by weight of rheological aid, 2 parts by weight of light stabilizer A, 1 part by weight of light stabilizer B and butyl acetate 6 Add another part by weight and disperse at high speed for 10 minutes.

(2) Preparation of component B of paint: 9.5 parts by weight of butyl acetate at room temperature, 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wanhwa Chemical Group Co., Ltd.), amine-terminated dimethicone (Waker Chemical (China) Co., Ltd. ) 10 parts by weight and 13.5 parts by weight of an adhesion promoter were added, mixed, and dispersed at high speed for 5 minutes.

(3) Form a paint by uniformly mixing the two components A and B described above at room temperature according to a weight ratio of 1:1.2.

Comparative Example 6 - A manufacturing process of a polyaspartate polyurea coating layer containing a fluorine-silicon-modified organic antifouling agent includes the following steps.

(1) Preparation of component A of paint: 42 parts by weight of fluorine silicon modified polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, dodecylbis(2-hydroxyethyl) at room temperature ) 10 parts by weight of methylammonium chloride, 10 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of desiccant, 0.2 parts by weight of antifoamer A and 0.15 parts by weight of antifoamer B were mixed and dispersed at high speed for 30 minutes and the dispersion speed is 1500 r/min, and then polished so that the particle size is less than 30 μm, and then 0.1 part by weight of leveling agent A, 0.1 part by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 part by weight of rheological auxiliary agent, 2 parts by weight of light stabilizer A, 1 part by weight of light stabilizer B and 6 parts by weight of butyl acetate were further added and dispersed at high speed for 10 minutes.

(2) Preparation of component B of paint: 9.5 parts by weight of butyl acetate, 0.5 part by weight of dehydrating agent, 76.5 parts by weight of polyisocyanate HT600 (Wanhwa Chemical Group Co., Ltd.) and 13.5 parts by weight of adhesion promoter were added and mixed at room temperature, followed by mixing at high speed for 5 minutes. Disperse.

(3) Form a paint by uniformly mixing the two components A and B described above at room temperature according to a weight ratio of 1:1.1.

Example 1 - A manufacturing process of a coating layer of an aspartic polyurea resin system containing a fluorosilicone-modified organic antifouling agent includes the following steps.

(1) Preparation of component A of paint: 48 parts by weight of fluorine silicon modified polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, dodecylbis(2-hydroxyethyl) at room temperature ) 5 parts by weight of methylammonium chloride, 5 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of desiccant, 0.2 parts by weight of antifoamer A and 0.15 parts by weight of antifoamer B were mixed and dispersed at high speed for 30 minutes and the dispersion speed is 1500 r/min, and then polished so that the particle size is less than 30 μm, and then 0.1 part by weight of leveling agent A, 0.1 part by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 part by weight of rheological auxiliary agent, 2 parts by weight of light stabilizer A and 1 part by weight of light stabilizer B were further added and dispersed at high speed for 10 minutes.

(2) Preparation of component B of paint: 0.5 parts by weight of dehydrating agent at room temperature, 66.5 parts by weight of polyisocyanate HT600 (Wanhwa Chemical Group Co., Ltd.), 10 parts by weight of amine-terminated dimethicone (Waker Chemical (China) Co., Ltd.) and adhesion 13.5 parts by weight of the accelerator are added, mixed, and dispersed at high speed for 5 minutes.

(3) A paint is formed by uniformly mixing the two components A and B described above at room temperature according to a weight ratio of 1:1.

Example 2 - The manufacturing process of the organic antifouling agent-containing aspartic polyurea resin system coating layer provided in Example 1 is basically the same as Example 1, with the differences as follows.

Preparation of component A of paint: 48 parts by weight of fluorine silicon modified polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, dodecylbis(2-hydroxyethyl)methylammonium at room temperature 10 parts by weight of chloride, 10 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of desiccant, 0.2 parts by weight of antifoaming agent A and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes. is 1500 r/min, and then polished so that the particle size is less than 30 μm, then 0.1 part by weight of leveling agent A, 0.1 part by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 part by weight of rheological auxiliary agent, light stabilizer A 2 parts by weight and 1 part by weight of light stabilizer B8 were further added and dispersed at high speed for 10 minutes.

Preparation of component B of paint: 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wanhwa Chemical Group Co., Ltd.), 10 parts by weight of amine-terminated dimethicone (Waker Chemical (China) Co., Ltd.) and adhesion promoter at 60 ° C. Add 13.5 parts by weight, mix, and disperse at high speed for 5 minutes.

At room temperature, the two components A and B were uniformly mixed according to a weight ratio of 1:1.5 to form a paint.

Example 3 - The manufacturing process of the organic antifouling agent-containing aspartic polyurea resin system coating layer provided in Example 1 is basically the same as Example 1, with differences as follows.

Preparation of component A of paint: 48 parts by weight of fluorine silicon modified polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, dodecylbis(2-hydroxyethyl)methylammonium at room temperature 20 parts by weight of chloride, 20 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of desiccant, 0.2 parts by weight of antifoaming agent A and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes. is 1500 r/min, and then polished so that the particle size is less than 30 μm, then 0.1 part by weight of leveling agent A, 0.1 part by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 part by weight of rheological auxiliary agent, light stabilizer A 2 parts by weight and 1 part by weight of light stabilizer B were further added and dispersed at high speed for 10 minutes.

Preparation of component B of paint: 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wanhwa Chemical Group Co., Ltd.), 10 parts by weight of amine-terminated dimethicone (Waker Chemical (China) Co., Ltd.) and adhesion promoter at 60 ° C. Add 13.5 parts by weight, mix, and disperse at high speed for 5 minutes.

A paint is formed by uniformly mixing the two components A and B described above at room temperature according to a weight ratio of 1:2.

Example 4 - The manufacturing process of the organic antifouling agent-containing aspartic polyurea resin system coating layer provided in Example 1 is basically the same as Example 1, with the differences as follows.

Preparation of component A of paint: 48 parts by weight of fluorine silicon modified polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, dodecylbis(2-hydroxyethyl)methylammonium at room temperature 30 parts by weight of chloride, 30 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of desiccant, 0.2 parts by weight of antifoaming agent A and 0.15 parts by weight of antifoaming agent B were mixed and dispersed at high speed for 30 minutes. is 1500 r/min, and then polished so that the particle size is less than 30 μm, then 0.1 part by weight of leveling agent A, 0.1 part by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 part by weight of rheological auxiliary agent, light stabilizer A 2 parts by weight and 1 part by weight of light stabilizer B were further added and dispersed at high speed for 10 minutes.

Preparation of component B of paint: 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wanhwa Chemical Group Co., Ltd.), 10 parts by weight of amine-terminated dimethicone (Waker Chemical (China) Co., Ltd.) and adhesion promoter at a temperature of 65 ° C. Add 13.5 parts by weight, mix, and disperse at high speed for 5 minutes.

A paint is formed by uniformly mixing the two components A and B described above at room temperature according to a weight ratio of 1:3.

Example 5 - The manufacturing process of the organic antifouling agent-containing aspartic polyurea resin system coating layer provided in Example 5 is basically the same as Example 1, with the differences as follows.

Preparation of component A of paint: 48 parts by weight of polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, 4-bromo-2-(4-chlorophenyl)-5 at room temperature -(Trifluoromethyl)-1Hpyrrole-3-carbonitrile (Econea) 10 parts by weight, polyethylene glycol monomethyl ether 10 parts by weight, filler 12 parts by weight, anti-sagging agent 0.3 parts by weight, desiccant 3 parts by weight, defoamer A 0.2 parts by weight Part by weight and 0.15 part by weight of antifoamer B were mixed, dispersed at high speed for 30 minutes, the dispersion speed was 1500 r/min, and then polished to have a particle size of less than 30 μm, then 0.1 part by weight of leveling agent A, 0.1 part by weight of leveling agent B, 1 part by weight of a silane coupling agent, 0.15 part by weight of a rheological aid, 2 parts by weight of light stabilizer A and 1 part by weight of light stabilizer B were further added and dispersed at high speed for 10 minutes.

Preparation of component B of paint: 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wanhwa Chemical Group Co., Ltd.), 10 parts by weight of amine-terminated dimethicone (Waker Chemical (China) Co., Ltd.) and adhesion promoter at 60 ° C. Add 13.5 parts by weight, mix, and disperse at high speed for 5 minutes.

At room temperature, the two components A and B were uniformly mixed according to a weight ratio of 1:1.5 to form a paint.

Example 6 - The manufacturing process of the organic antifouling agent-containing aspartic polyurea resin system coating layer provided in the above example is basically the same as that of Example 1, with differences as follows.

Preparation of component A of paint: 48 parts by weight of silicon-containing polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 2 parts by weight of dispersant, 10 parts by weight of pigment, N-(2,4,6-trichloro) at 40 ° C. 10 parts by weight of phenyl) maleimide (TCM), 10 parts by weight of polyethylene glycol monomethyl ether, 12 parts by weight of filler, 0.3 parts by weight of anti-sagging agent, 3 parts by weight of desiccant, 0.2 parts by weight of antifoamer A and 0.15 parts by weight of antifoamer B were mixed and 30 parts by weight Minutes of high-speed dispersion, the dispersion speed is 1500 r/min, and then polished so that the particle size is less than 30 μm, 0.1 part by weight of leveling agent A, 0.1 part by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 part by weight of rheological auxiliary agent By weight, 2 parts by weight of light stabilizer A and 1 part by weight of light stabilizer B were further added and dispersed at high speed for 10 minutes.

Preparation of B component of paint: 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wanhwa Chemical Group Co., Ltd.), 10 parts by weight of amine-terminated dimethicone (Waker Chemical (China) Co., Ltd.) and adhesion promoter at 80 ° C temperature Add 13.5 parts by weight, mix, and disperse at high speed for 5 minutes.

A paint is formed by uniformly mixing the two components A and B described above at a temperature of 40° C. according to a weight ratio of 1:1.5.

Example 7 - The manufacturing process of the organic antifouling agent-containing aspartic polyurea resin system coating layer provided in the above example is basically the same as that of Example 1, and the differences are as follows.

Preparation of component A of paint: 48 parts by weight of fluorine-containing polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 2 parts by weight of dispersant, 20 parts by weight of pigment, 0.1 part by weight of medetomidine, 10 parts by weight of polyethylene glycol monomethyl ether at room temperature Part by weight, 12 parts by weight of filler, 0.3 part by weight of anti-sagging agent, 3 parts by weight of desiccant, 0.2 part by weight of antifoamer A and 0.15 part by weight of antifoamer B were mixed and dispersed at high speed for 30 minutes. After polishing to less than ㎛, 0.1 parts by weight of leveling agent A, 0.1 part by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 part by weight of rheological auxiliary agent, 2 parts by weight of light stabilizer A and 1 part by weight of light stabilizer B further Add and disperse at high speed for 10 minutes.

Preparation of component B of paint: 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wanhwa Chemical Group Co., Ltd.), 10 parts by weight of amine-terminated dimethicone (Waker Chemical (China) Co., Ltd.) and adhesion promoter at 60 ° C. Add 13.5 parts by weight, mix, and disperse at high speed for 5 minutes.

A paint is formed by uniformly mixing the two components A and B described above at a temperature of 50° C. according to a weight ratio of 1:1.2.

Example 8 - The manufacturing process of the organic antifouling agent-containing aspartic polyurea resin system coating layer provided in the above example is basically the same as that of Example 1, with differences as follows.

Preparation of component A of the paint: 48 parts by weight of polyaspartate resin (Nanjing Lanfeng New Material Technology Co., Ltd.), 2 parts by weight of dispersant, 20 parts by weight of pigment, 10 parts by weight of copper pyrithione, 10 parts by weight of polyethylene glycol monomethyl ether at room temperature , 12 parts by weight of filler, 0.3 part by weight of anti-sagging agent, 3 parts by weight of moisture retardant, 0.2 part by weight of antifoamer A and 0.15 part by weight of antifoamer B were mixed and dispersed at high speed for 30 minutes, the dispersion speed was 1500r/min, and then the particle size was less than 30㎛ Then, 0.1 part by weight of leveling agent A, 0.1 part by weight of leveling agent B, 1 part by weight of silane coupling agent, 0.15 part by weight of rheological aid, 2 parts by weight of light stabilizer A, and 1 part by weight of light stabilizer B were further added. High speed dispersion for 10 minutes.

Preparation of component B of paint: 0.5 parts by weight of dehydrating agent, 66.5 parts by weight of polyisocyanate HT600 (Wanhwa Chemical Group Co., Ltd.), 10 parts by weight of amine-terminated dimethicone (Waker Chemical (China) Co., Ltd.) and adhesion promoter at 60 ° C. Add 13.5 parts by weight, mix, and disperse at high speed for 5 minutes.

At room temperature, the two components A and B were uniformly mixed according to a weight ratio of 1:1.5 to form a paint.

The coating layers of Comparative Example 1, Comparative Example 2, and Example 1 were composed of unmodified polyurea PUA, fluorine-silicon-modified polyurea PUA-FSi, and organic antifouling agent-containing polyurea PUA-FSi-N, respectively, and their infrared spectrums were respectively As shown in Figures 1, 2 and 3. In FIG. 1, PUA (A) is an unmodified aspartic polyurea resin, PUA (B) is an unmodified aspartic polyurea resin curing agent, and PUA is formed by mixing and curing PUA (A) and PUA (B). it did In FIG. 2, PUA-FSi (A) is a fluorosilicone-modified aspartic polyurea resin, PUA (B) is a fluorosilicon-modified aspartic polyurea resin curing agent, and PUA is a combination of PUA-FSi (A) and PUA (B). It is formed by mixing and curing. In FIG. 3, PUA-FSi-N (A) is a fluorosilicone-modified aspartic polyurea resin, PUA-FSi-N (B) is a fluorosilicon-modified aspartic polyurea resin curing agent, and PUA-FSi-N is a PUA- It is formed by mixing and curing FSi-N (A), an organic quaternary ammonium salt, and PUA-FSi-N (B). As can be seen from FIGS. 1 to 3, after curing for 3 days, each of the obtained coating layers completely lost the u-NCO = 2267 cm ^-1 characteristic peak, and formed a urea-bonded u-NH = 1658 cm ^-1 characteristic peak , which proves that the coating layer is completely cured.

4, 5, and 6 are photographs of water contact angles of coating layers of Comparative Example 1, Comparative Example 2, and Example 1, respectively. As a control, an antifouling coating layer was formed using a commercially available organic silicon antifouling paint according to the conditions of Example 1, and the water contact angle photograph is shown in FIG. 7 . As can be seen here, the water contact angle of the fluorosilicone-modified polyurea PUA-FSi increased from 90.5 degrees to 108.8 degrees of the unmodified polyurea PUA, and the contact angle of the organic silicon antifouling coating layer (PDMS coating layer) formed of a commercially available organic silicon antifouling paint was 112.9 degrees. relatively close to This indicates that the fluorosilicon-modified polyurea PUA-FSi is a low surface energy coating layer with excellent performance. The water contact angle of PUA-FSi-N, a polyurea containing an organic antifouling agent grafted with an antifouling group, decreased from 108.8 degrees to 61.7 degrees. This may indicate that a hydrophilic hydrogel is formed on the surface of the coating layer based on the fluorine-silicon-modified polyurea PUA-FSi, and may further reflect the abundance of organic antifouling agents on the surface of the coating layer.

Furthermore, the organic silicon antifouling coating layer (PDMS) formed by the above-described unmodified polyurea PUA, fluorine silicon modified polyurea PUA-FSi, organic antifouling agent-containing polyurea PUA-FSi-N coating layer and commercially available organic silicon antifouling paint The water contact angle test results may further refer to FIG. 8 .

FIG. 9 shows a comparison of the above-described unmodified polyurea PUA, fluorine silicon-modified polyurea PUA-FSi, organic antifouling agent-containing polyurea PUA-FSi-N coating layer, and PDMS coating layer and epoxy primer adhesive strength. As can be seen from this, the organic silicon antifouling coating layer with the organic antifouling agent-containing polyurea PUA-FSi-N coating layer and the epoxy primer have excellent adhesion, which is 50 times that of the organic silicon antifouling coating layer without using the epoxy primer. This can shorten the actual construction process and further reduce the construction cost.

10 and 11 compare mechanical performances such as stress-strain and Young's modulus of the aforementioned unmodified polyurea PUA, fluorine-silicon-modified polyurea PUA-FSi, organic antifouling agent-containing polyurea PUA-FSi-N coating layer, and PDMS coating layer, respectively. it did As can be seen from the drawing, the organic antifouling agent-containing polyurea PUA-FSi-N coating layer has excellent mechanical properties, Young's modulus is 1400 times that of the PDMS coating layer, and the scratch resistance of the coating layer is greatly improved.

The properties of the paints obtained from Comparative Examples 1 to 5 and Examples 1 to 8 and the coating layers formed therefrom are shown in Table 1 and Table 2, respectively.

Table 1: Paint Properties

Table 2: Coating layer properties

In each of the above Examples and Comparative Examples, each paint and coating layer property test method was performed with reference to national standards GB/T 6822-2014 and HG/T 3831-2006. Here, the "chemical resistance" test items in Table 2 are basic resistance 240h (3% NaCl solution), alkali resistance 240h (5% NaOH solution), acid resistance 240h (5% H ₂ SO ₄ solution), water resistance 30 days (25 ℃ )am.

Example 9 - A method for synthesizing an aspartic polyurea resin system having marine antifouling function includes the following steps. At room temperature, 66.5 parts by weight of polyisocyanate HT600 (Wanhua Chemical Group Co., Ltd.) and 10 parts by weight of amine-terminated dimethicone (Wanke Chemical (China) Co., Ltd.) were mixed and dispersed at high speed for 5 minutes, followed by fluorine-silicon-modified polyaspartate. 42 parts by weight of resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 5 parts by weight of dodecylbis(2-hydroxyethyl)methylammonium chloride, and 5 parts by weight of polyethylene glycol monomethyl ether were added, followed by high-speed dispersion for 10 minutes to obtain the target product Acquire The infrared spectrum of the target product is similar to that of PUA-FSi-N in Example 1.

Example 10 - A method for synthesizing an aspartic polyurea resin system with marine antifouling function includes the following steps. 66.5 parts by weight of polyisocyanate HT600 (Wanhua Chemical Group Co., Ltd.) and 10 parts by weight of amine-terminated dimethicone (Wanke Chemical (China) Co., Ltd.) were mixed at 60 ° C. Mixed with 42 parts by weight of fluorine silicon modified polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.), 10 parts by weight of dodecylbis(2-hydroxyethyl)methylammonium chloride, and 10 parts by weight of polyethylene glycol monomethyl ether at room temperature , followed by high-speed dispersion for 30 minutes to obtain the target product.

Example 11 - A method for synthesizing an aspartic polyurea resin system having a marine antifouling function includes the following steps. 66.5 parts by weight of polyisocyanate HT600 (Wanhua Chemical Group Co., Ltd.) and 10 parts by weight of amine-terminated dimethicone (Wanke Chemical (China) Co., Ltd.) were mixed at 80 ° C. 42 parts by weight of polyaspartate resin (Nanjing Lanfeng New Materials Technology Co., Ltd.) at room temperature, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1Hpyrrole-3-carbonitrile ( Econea) 10 parts by weight and polyethylene glycol monomethyl ether 10 parts by weight, followed by high-speed dispersion for 30 minutes to obtain the target product.

Each performance of the target products of Examples 9 to 11 was tested according to the method of Examples 1 to 8, and it was found that they were all excellent in terms of elongation at break, water contact angle, surface energy, abrasion resistance, and antifouling performance.

The above is only a preferred embodiment of the present application and does not limit the present application. A person skilled in the art may improve and replace parts without departing from the technical principles of the present application, and such improvements and replacements fall within the protection scope of the present application.

Claims (12)

In the aspartic polyurea resin system having a marine antifouling function,
Including a polymer having a structure represented by the following formula,

Here, X is derived from a polyaspartate resin, Y is derived from an isocyanate curing agent, and R is a group having an antibacterial and antifouling function. In the aspartic polyurea resin system having a marine antifouling function,
An aspartic polyurea resin system with marine antifouling function, characterized in that it is formed by reaction of polyaspartate resin, organic antifouling agent, polyether, polyisocyanate and organic silicone resin. According to claim 2,
the polyaspartate resin includes a combination of any one or more of a polyaspartate resin, a fluorine-containing polyaspartate resin, a silicon-containing polyaspartate resin, and a fluorine-silicon-containing modified polyaspartate resin;
The organic antifouling agent is 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1Hpyrrole-3-carbonitrile, 4-bromo-2-(4-chlorophenyl)- 5-(trifluoromethyl)-1Hpyrrole-3-carbonitrile derivatives, N-(2,4,6-trichlorophenyl)maleimide, copper pyrithione, zinc pyrithione, medetomidine, medetomidine Derivatives, butenolides, butenolide derivatives, alkyl dimethyl benzyl quaternary ammonium salts, trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, dimethyl includes a combination of any one or more of octadecyl(3-trimethoxysilylpropyl)ammonium chloride, dodecylbis(2-hydroxyethyl)methylammonium chloride, and bis(2-hydroxyethyl)methyltetradecylammonium chloride; do or;
the polyether comprises a combination of any one or more of polyethylene glycol, polyethylene glycol monomethyl ether, poly(ethylene glycol)methyl ether amine, polypropylene glycol, polypropylene glycol monomethyl ether, and polyether amine;
the organic silicone resin comprises a combination of any one or more of the compounds listed below;

wherein n is from 10 to 1000;
The polyisocyanate is hexamethylene diisocyanate trimer, fluorine silicon modified hexamethylene diisocyanate trimer, L-lysine triisocyanate, fluorine silicon modified L-lysine triisocyanate, triphenylmethane triisocyanate, fluorine silicon modified triphenylmethane triisocyanate Aspartic polyurea resin system having a marine antifouling function, characterized in that it comprises a combination of at least one or more of. In the paint composition,
A coating composition comprising the aspartic polyurea resin system according to any one of claims 1 to 3. According to claim 4,
The aspartic polyurea resin system accounts for 0.5% to 99% of the dry film weight of the coating composition, or the sum of the masses of the aspartic polyurea resin system and the one or more antifouling agents is 0.5% to 99% of the dry film weight of the coating composition. % and/or the coating composition is a solvent-free system. In the paint composition,
Raw materials of the coating composition include 0 to 80 parts by weight of polyaspartate resin, 0 to 50 parts by weight of organic antifouling agent, 0 to 50 parts by weight of polyether, 0 to 80 parts by weight of organic silicone resin, and 20 to 100 parts by weight of polyisocyanate. wherein the capacities of the polyaspartate resin, the organic antifouling agent, the polyether, and the organic silicone resin are all greater than zero. According to claim 6,
The polyaspartate resin has the following structure,

Here, R ₁ is selected from an aliphatic hydrocarbon group, preferably a C1-C100 aliphatic hydrocarbon group, and R ₂ is selected from a hydrocarbon group containing fluorine or silicon, preferably a hydrocarbon group containing C1-C100 fluorine or silicon. A coating composition characterized in that it becomes. According to claim 6,
the polyaspartate resin includes a combination of any one or more of a polyaspartate resin, a fluorine-containing polyaspartate resin, a silicon-containing polyaspartate resin, and a fluorine-silicon-containing modified polyaspartate resin;
The organic antifouling agent is 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1Hpyrrole-3-carbonitrile, 4-bromo-2-(4-chlorophenyl)- 5-(trifluoromethyl)-1Hpyrrole-3-carbonitrile derivatives, N-(2,4,6-trichlorophenyl)maleimide, copper pyrithione, zinc pyrithione, medetomidine, medetomidine Derivatives, butenolides, butenolide derivatives, alkyl dimethyl benzyl quaternary ammonium salts, trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, dimethyl includes a combination of any one or more of octadecyl(3-trimethoxysilylpropyl)ammonium chloride, dodecylbis(2-hydroxyethyl)methylammonium chloride, and bis(2-hydroxyethyl)methyltetradecylammonium chloride; do or;
the polyether comprises a combination of any one or more of polyethylene glycol, polyethylene glycol monomethyl ether, poly(ethylene glycol)methyl ether amine, polypropylene glycol, polypropylene glycol monomethyl ether, and polyether amine;
the organic silicone resin comprises a combination of any one or more of the compounds listed below;

wherein n is from 10 to 1000;
The polyisocyanate is hexamethylene diisocyanate trimer, fluorine silicon modified hexamethylene diisocyanate trimer, L-lysine triisocyanate, fluorine silicon modified L-lysine triisocyanate, triphenylmethane triisocyanate, fluorine silicon modified triphenylmethane triisocyanate A coating composition characterized in that it comprises a combination of at least one or more of. According to claim 6,
The coating composition, characterized in that the raw material of the coating composition further comprises a combination of any one or more of a filler and an auxiliary agent, and/or the coating composition is a solvent-free system. According to claim 9,
The raw material of the coating composition further includes 0 to 50 parts by weight of a filler and 0 to 20 parts by weight of an auxiliary agent;
the filler comprises a combination of any one or more of iron sulfur oxide, barium sulfate, titanium dioxide, silicon fine powder, talc powder, and heavy calcium;
The coating composition, characterized in that the auxiliary agent comprises a combination of any one or more of a leveling agent, an antifoaming agent, a dispersing agent, a thickening agent, a coupling agent, and an activating powder. In the method for producing a coating composition,
mixing raw materials according to the raw material composition of the coating composition according to any one of claims 6 to 10; and
A manufacturing method comprising mixing polyisocyanate and organic silicone resin, reacting at 0 to 80° C. in a protective gas atmosphere, and then uniformly mixing with the remaining raw materials to form a coating composition. A coating layer formed of the coating composition according to any one of claims 4 to 10.

Images